Intramolecular Singlet Fission Research Articles

Spin Mixing in Intramolecular Singlet Fission: A First-Principles-Based Quantum Dynamical Study.

We investigate the dynamical interplay between the different triplet-pair spin states that are formed in the intramolecular singlet fission process in a series of pentacene-based dimers covalently bonded to a phenylene linker in ortho, meta, and para positions. Using first-principles calculations and a density matrix quantum dynamical approach we show that the spin dipole-dipole interaction leads to significant population of the quintet spin manifold in these regioisomers when the singlet, triplet and quintet triplet-pair states are quasidegenerate. Furthermore, we also show that the relative arrangement of the pentacene-like moieties has a profound impact on the dynamics of the spin-mixing process, affecting both the relative population of the different spin-states involved in the dynamics and the time scale of the process.

The Interplay of Strongly and Weakly Exchange-Coupled Triplet Pairs in Intramolecular Singlet Fission.

Singlet fission (SF) and triplet-triplet annihilation upconversion (TTA-UC) nominally enable the interconversion of higher-energy singlet states with two lower-energy triplet states and vice versa, with both processes having envisaged application for enhanced solar power devices. The mechanism of SF/TTA-UC involves a complex array of different multiexcitonic triplet-pair states that are coupled by the exchange interaction to varying extents. In this work a family of bounded intramolecular SF materials, based upon the chromophore 1,6-diphenyl-1,3,5-hexatriene, were designed and synthesized. Their SF behavior was characterized using fluorescence lifetime, transient absorption, and magnetic field dependence studies. The capacity for the formation of weakly exchange-coupled triplet pairs, and subsequent spin-evolution, is shown to be strongly dependent upon the combined factors of oligomer size and geometry. By contextualizing these results with the wider SF literature, we present a general schematic model for SF/TTA-UC of greater completeness than portrayed elsewhere.

The Acetylene Bridge in Intramolecular Singlet Fission: A Boon or A Nuisance?

Various analogues of the alkylsilylacetylene group are frequently used as auxiliary groups to enhance the solubility and stability of the acene dimer core, widely used as platforms to investigate intramolecular singlet fission (iSF) mechanisms. However, while in the 2,2'-linked dimers they are primarily auxiliary groups, these are essential fragments of the bridging units in 6,6'/5,5'-linked dimers, the two preferred choices for dimerization. The starkly different iSF dynamics observed in the two variants raise the question of what role the acetylene bridges play. Here, we systematically designed a set of (oligo-)para-phenylene bridged 2,2'-linked pentacene dimers with an additional acetylene fragment in the bridging unit to mimic the structure of 6,6'-linked dimers. Contrasting the results with previously reported analogous 2,2'-linked and 6,6'-linked pentacene dimers reveals that the acetylene bridges contribute to significant conformational freedom. This effect provides a mechanism to promote spin evolution within the triplet pair to achieve free triplets but also offers new parasitic pathways for triplet-pair recombination, revealing that this structural motif can be both a boon and a nuisance. Additionally, our analysis reveals that these bridges directly modify the electronic states, highlighting significant pitfalls of the standard chromophore-bridge-chromophore framework used to design and interpret photophysics of iSF materials.

The Acetylene Bridge in Intramolecular Singlet Fission: A Boon or A Nuisance?

Various analogues of the alkylsilylacetylene group are frequently used as auxiliary groups to enhance the solubility and stability of the acene dimer core, widely used as platforms to investigate intramolecular singlet fission (iSF) mechanisms. However, while in the 2,2’‐linked dimers they are primarily auxiliary groups, these are essential fragments of the bridging units in 6,6’/5,5’‐linked dimers, the two preferred choices for dimerization. The starkly different iSF dynamics observed in the two variants raise the question of what role the acetylene bridges play. Here, we systematically designed a set of (oligo‐)para‐phenylene bridged 2,2’‐linked pentacene dimers with an additional acetylene fragment in the bridging unit to mimic the structure of 6,6’‐linked dimers. Contrasting the results with previously reported analogous 2,2’‐linked and 6,6’‐linked pentacene dimers reveals that the acetylene bridges contribute to significant conformational freedom. This effect provides a mechanism to promote spin evolution within the triplet pair to achieve free triplets but also offers new parasitic pathways for triplet‐pair recombination, revealing that this structural motif can be both a boon and a nuisance. Additionally, our analysis reveals that these bridges directly modify the electronic states, highlighting significant pitfalls of the standard chromophore‐bridge‐chromophore framework used to design and interpret photophysics of iSF materials.

Strong-Coupling Modification of Singlet-Fission Dynamical Pathways.

We investigate theoretically the influence of strong light-matter coupling on the initial steps of the phototriggered singlet-fission process. In particular we focus on intramolecular singlet fission in a TIPS-pentacene dimer derivative described by a vibronic Hamiltonian including the optically active singlet excited states, doubly excited and charge transfer states, as well as the final triplet-triplet pair state. Quantum dynamics simulations of up to four dimers in the cavity indicate that the modified resonance condition imposed by the cavity strongly quenches the passage through the intermediate charge transfer and double-excitation states, thus largely reducing the triplet-triplet yield in the bare system. Subsequently, we modify the system parameters and construct a model Hamiltonian where the optically active singlet excitation lies below the final triplet-triplet state such that the yield of the bare system becomes insignificant. In this case we find that using the upper polariton as the doorway state for photoexcitation can lead to a much enhanced yield. This pathway is operative provided that the system is sufficiently rigid to prevent vibronic losses from the upper polariton to the dark-states manifold.

Ultrafast Intramolecular Singlet Fission in Homoconjugated Oligomers of Azapentacene with Rigid Connecting Unit

Ultrafast Intramolecular Singlet Fission in Homoconjugated Oligomers of Azapentacene with Rigid Connecting Unit

Intramolecular singlet fission: Quantum dynamical simulations including the effect of the laser field.

In the previous work [Reddy et al., J. Chem. Phys. 151, 044307 (2019)], we have analyzed the dynamics of the intramolecular singlet fission process in a series of prototypical pentacene-based dimers, where the pentacene monomers are covalently bonded to a phenylene linker in ortho, meta, and para positions. The results obtained were qualitatively consistent with the experimental data available, showing an ultrafast population of the multiexcitonic state that mainly takes place via a mediated (superexchange-like) mechanism involving charge transfer and doubly excited states. Our results also highlighted the instrumental role of molecular vibrations in the process as a sizable population of the multiexcitonic state could only be obtained through vibronic coupling. Here, we extend these studies and investigate the effect of the laser field on the dynamics of intramolecular singlet fission by explicitly including the coupling to the laser field in our model. In this manner, and by selectively tuning the laser field to the different low-lying absorption bands of the systems investigated, we analyze the wavelength dependence of the intramolecular singlet fission process. In addition, we have also analyzed how the nature of the initially photoexcited electronic state (either localized or delocalized) affects its dynamics. Altogether, our results provide new insights into the design of intramolecular singlet fission-active molecules.

Intramolecular Singlet Fission Coupled with Intermolecular Triplet Separation as a Strategy to Achieve High Triplet Yields in Fluorene-Based Small Molecules.

In this work, detailed experimental proof and in-depth analysis of the singlet fission (SF) mechanism, operative in fluorene-based small molecules, are carried out by employing advanced time-resolved spectroscopies with nanosecond and femtosecond resolution. The investigation of the effect of solution concentration and solvent viscosity together with temperature and excitation wavelength demonstrates INTRAmolecular formation of the correlated triplet pair followed by INTERmolecular independent triplet separation via a "super-diffusional" triplet-triplet transfer process. This unconventional INTRA- to INTERmolecular SF may be considered an "ideal" mechanism. Indeed, intramolecular formation of the correlated triplet pair is here interestingly proved for small molecules rather than large multichromophoric systems, allowing easy synthesis and processability while maintaining good control over the SF process. On the other hand, the intermolecular triplet separation may be exploited to achieve high triplet quantum yields in these new SF small molecules.

Simultaneous Intra- and Intermolecular Singlet Fission in Bipentacene Macrocycle Aggregates.

Singlet fission (SF) is a process where a singlet state splits into two triplet states, which is essential for enhancing optoelectronic devices. Macrocyclic structures allow for precise control of chromophore orientation and facilitate singlet fission in solutions. However, the behavior of these structures in thin films, crucial for solid-state device optimization, remains underexplored. This study examines the aggregation and singlet fission processes of bipentacene macrocycles (BPc) in thin films using molecular dynamics simulations and electronic structure calculations. Findings indicate that BPc aggregates more rapidly with less chloroform, aligning parallel to the substrate. Intramolecular singlet fission (iSF) rates are rarely changed during evaporation, but the efficiency of intermolecular singlet fission (xSF) improves due to the increase in packing domains, suggesting that orderly crystal domains are not necessary for device efficiency. This opens avenues for varied device designs and traditional solution-based methods for optimal device development.

The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene‐Bridged Pentacene Dimers

AbstractA series of ferrocene(Fc)‐bridged pentacene(Pc)‐dimers [Fc−Ph(2,n)−(Pc)2: n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc‐terminated phenylene linkers on strongly coupled quintet multiexciton (5TT) formation through intramolecular singlet fission (ISF). Fc−Ph(2,4)−(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc−Ph(2,4)−(Pc)2 exhibits a high‐yield 5TT together with quantitative singlet TT (1TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1TT spin conversion of Fc−Ph(2,4)−(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1TT is attributable to weakened metal‐ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1TT unpaired orbitals.

The Effect of Torsional Motion on Multiexciton Formation through Intramolecular Singlet Fission in Ferrocene-Bridged Pentacene Dimers.

A series of ferrocene(Fc)-bridged pentacene(Pc)-dimers [Fc-Ph(2,n)-(Pc)2 : n=number of phenylene spacers] were synthesized to examine the tortional motion effect of Fc-terminated phenylene linkers on strongly coupled quintet multiexciton (5 TT) formation through intramolecular singlet fission (ISF). Fc-Ph(2,4)-(Pc)2 has a relatively small electronic coupling and large conformational flexibility according to spectroscopic and theoretical analyses. Fc-Ph(2,4)-(Pc)2 exhibits a high-yield 5 TT together with quantitative singlet TT (1 TT) generation through ISF. This demonstrates a much more efficient ISF than those of other less flexible Pc dimers. The activation entropy in 1 TT spin conversion of Fc-Ph(2,4)-(Pc)2 is larger than those of the other systems due to the larger conformational flexibility associated with the torsional motion of the linkers. The torsional motion of linkers in 1 TT is attributable to weakened metal-ligand bonding in the Fc due to hybridization of the hole level of Pc to Fc in 1 TT unpaired orbitals.

Survey of T1 and T2 Energies of Intramolecular Singlet Fission Chromophores

Singlet fission is a desired process in photovoltaics since it enhances photoelectric conversion efficiency. Intramolecular singlet fission is of special interest as the fission efficiency can be improved through tuning configurations between chromophore units that are covalently connected. However, intramolecular singlet fission chromophores feature a large tetraradical character, and may tend to dissatisfy the ET2>2ET1 criterion for all singlet fission chromophores, intramolecular or not. We performed spin-flip time-dependent density functional theory calculations for a collection of representative intramolecular singlet fission chromophores to show that this is indeed the case.

Tetracene cyclophanes showing controlled intramolecular singlet fission by through-space orientations.

Tetracene cyclophanes: a series of cyclic tetracene dimers bridged by two flexible ethylene glycol units demonstrated enhanced intramolecular singlet fission through through-space orientations by suppressing the H-type excited complex.

Investigation of excited states of BODIPY derivatives and non-orthogonal dimers from the perspective of singlet fission.

We report state of the art electronic structure calculations RICC2 and XMCQDPT of BODIPY nonorthogonal dimers to understand the photophysical processes from the intramolecular singlet fission (iSF) perspective. We have calculated singlet, triplet and quintet states at the XMCQDPT(8,8)/cc-pVDZ level of theory and diabatic singlet states at the XMCQDPT(4,4)/cc-pVDZ level of theory. In all the systems studied, charge transfer states (1(CA) and 1(AC)) couple strongly with locally excited (1(S1S0)) and multiexcitonic (1(T1T1)) states. The rates of formation of the multiexcitonic state from the locally excited state are very low on account of large activation energy (E(1(T1T1)) - E(1(S1S0))). A relaxed scan along the torsional angle revealed contrasting results for axial and orthogonal conformers. We proposed a probable mechanism for contrasting photophysical properties of dimers B[3,3] and B[2,8]. We also found that substitution of CN, NH2 and BH2 at meso, β and α positions reduces the energy gap (ΔSF = 2E(T1) - E(S1)) significantly, making iSF a competing process in triplet state generation. Intrigued by the success of the CN group at the meso position in reducing the energy gap, we also studied the azaBODIPY monomer and its derivatives using the same methodology. The iSF is slightly endoergic with ΔSF ∼ 0.2 eV in these systems and iSF may play an important role in their photophysical responses.

Diverse quantum interference regimes in intramolecular singlet fission chromophores with thiophene-based linkers.

An array of thiophene-based π-conjugated linkers in covalently linked pentacene dimers allow us to access diverse quantum interference (QI), modulating nonadiabatic coupling (NAC) in the singlet fission (SF) process. Simulations show that structural isomerism in terms of S atom orientation substantially alters NAC with relatively marginal impacts on energies. Extended curly arrow rules (ECARs) reveal sensitive dependence of QI on SF linker topologies and connectivity, categorizing regimes of constructive, destructive, and previously unrealized in SF research, shifted destructive QI. Drastic NAC changes in terms of S atom orientation are rationalized based on the nature of QI. Our results from nonequilibrium Green's function calculation using density functional theory corroborate the classification of QI regimes based on ECARs. Moreover, we found that the extent of charge resonance contribution in electronic states relevant to multiexciton formation and the appearance of optically allowed charge transfer excitation strongly depends on the operative QI regime. Notably, the magnitude of NAC effectively captures this influence. Our findings show that QI can rationalize and semi-quantitatively correlate with NAC for the multiexciton formation step in the SF process.

The Lack of Triplet Fusion for an Intramolecular Singlet Fission Chromophore: The Expected, the Unexpected, and a Reconciliation.

Singlet fission (SF) has the potential to play a key role in photovoltaics since it generates a larger number of longer-lived triplet excitons after photoabsorption. Intramolecular SF (iSF) is of special interest since it enables tuning of SF efficiency by adjusting interchromophore configuration through covalent interaction. However, as elaborated in the present work, iSF chromophores are doomed to dissatisfy one general thermodynamic criterion for all SF chromophores, intramolecular or not: E(T2) ≥ 2E(T1), and therefore, the fusion of two triplet excitons to one triplet exciton is thermodynamically favorable. In our nonadiabatic quantum dynamics simulation for a model iSF chromophore, this expected fusion does not occur, because of the inefficient intersystem crossing hidden under the cover of internal conversion of the triplet fusion. A reconciliation is achieved between the dissatisfaction of E(T2) ≥ 2E(T1) and the large tetraradical character for general iSF chromophores.

Catalyzing Singlet Fission by Transition Metals: Second versus Third Row Effects.

The synthesis and characterization of platinum(II) and palladium(II) complexes bearing two (dimers Pt(Lpc)2Cl2 and Pd(Lpc)2Cl2), one (monomers Pt(Lpc)(Lref)Cl2 and Pd(Lpc)(Lref)Cl2), or no (reference compounds Pt(Lref)2Cl2 and Pd(Lref)2Cl2) pentacene-based pyridyl ligands are presented. Photophysical properties of the dimers are probed by means of steady-state and time-resolved transient absorption measurements in comparison to the monomer and model compounds. Our results document that despite enhanced spin-orbit coupling from the presence of heavy atoms, intramolecular singlet fission (iSF) is not challenged by intersystem crossing. iSF thus yields correlated triplet pairs and even uncorrelated triplet excited states upon decoherence. Importantly, significant separation of the two pentacenyl groups facilitates decoupling of the two chromophores. Furthermore, the mechanism of iSF is altered depending on the respective metal center, that is, Pt(II) versus Pd(II). The dimer based on Pt(II), Pt(Lpc)2Cl2, exhibits a direct pathway for the iSF and forms a correlated triplet pair with singlet-quintet spin-mixing within 10 ns in variable solvents. On the other hand, the dimer based on Pd(II), Pd(Lpc)2Cl2, leads to charge transfer mixing during the population of the correlated triplet pair that is dependent on solvent polarity. Moreover, Pd(Lpc)2Cl2 gives rise to a stable equilibrium between singlet and quintet correlated triplet pairs with lifetimes of up to 170 ns. Inherent differences in the size and polarizability, when contrasting platinum(II) with palladium(II), are the most likely rationale for the underlying trends.

Re-Thinking Dimer Design Principles with Indolonaphthyridine Intramolecular Singlet Fission.

Singlet fission is a phenomenon that could significantly improve the efficiency of photovoltaic devices. Indolonaphthyridine thiophene (INDT) is a photostable singlet fission material that could potentially be utilised in singlet fission-based photovoltaic devices. This study investigates the intramolecular singlet fission (i-SF) mechanism of INDT dimers linked via para-phenyl, meta-phenyl and fluorene bridging groups. Using ultra-fast spectroscopy the highest rate of singlet fission is found in the para-phenyl linked dimer. Quantum calculations show the para-phenyl linker encourages enhanced monomer electronic coupling. Increased rates of singlet fission were also observed in the higher polarity o-dichlorobenzene, relative to toluene, indicating that charge-transfer states have a role in mediating the process. The mechanistic picture of polarisable singlet fission materials, such as INDT, extends beyond the traditional mechanistic landscape.

Controlling Intramolecular Singlet Fission Dynamics via Torsional Modulation of Through-Bond versus Through-Space Couplings.

Covalent dimers, particularly pentacenes, are the dominant platform for developing a mechanistic understanding of intramolecular singlet fission (iSF). Numerous studies have demonstrated that a photoexcited singlet state in these structures can rapidly and efficiently undergo exciton multiplication to form a correlated pair of triplets within a single molecule, with potential applications from photovoltaics to quantum information science. One of the most significant barriers limiting such dimers is the fast recombination of the triplet pair, which prevents spatial separation and the formation of long-lived triplet states. There is an ever-growing need to develop general synthetic strategies to control the evolution of triplets following iSF and enhance their lifetime. Here, we rationally tune the dihedral angle and interchromophore separation between pairs of pentacenes in a systematic series of bridging units to facilitate triplet separation. Through a combination of transient optical and spin-resonance techniques, we demonstrate that torsion within the linker provides a simple synthetic handle to tune the fine balance between through-bond and through-space interchromophore couplings that steer iSF. We show that the full iSF pathway from femtosecond to microsecond timescales is tuned through the static coupling set by molecular design and structural fluctuations that can be biased through steric control. Our approach highlights a straightforward design principle to generate paramagnetic spin pair states with higher yields.

Efficient Intramolecular Singlet Fission in Spiro-Linked Heterodimers.

We investigate intramolecular singlet fission (iSF) of spiro-linked azaacene heterodimers by time-resolved spectroscopy and quantum chemical calculations. Combining two different azaacenes through a nonconjugated linker using condensation chemistry furnishes azaacene heterodimers. Compared to their homodimers, iSF quantum yields are improved at an extended absorption range. The driving force of iSF, the energy difference ΔEiSF between the S1 state and the correlated triplet pair 1(TT), is tuned by the nature of the heterodimers. iSF is exothermic in all of the herein studied molecules. The overall quantum yield for triplet exciton formation reaches approximately 174%. This novel concept exploits large energy differences between singlet electronic states in combination with spatially fixed chromophores, which achieves efficient heterogeneous iSF, if the through-space interaction between the chromophores is minimal.